Hydrogenation of

The course of the hydrogenation of [5]- and [6]metacyclophane (1b and 1c) and their thermochemistry is described. Both compounds are hydrogenated rapidly (within 10 s) to furnish the bridgehead olefins 13b and 12c. The accompanying hydrogenation enthalpies are -220 and -141 kJmol(-1), respectively. Strain energies (SE) and olefinic strains (OS) of a number of bridgehead olefins have been evaluated by DFT calculations; it was concluded that 13b belongs to the class of hyperstable olefins which correlates nicely with its reluctance to undergo hydrogenation. By combining experimental hydrogenation enthalpies and DFT calculations, SE of 187 and 121 kJmol(-1) were derived for 1b and 1c.     

The phase diagram and electrical characteristics of silver iodo-phosphate fast-ion electrolytes

The equilibrium phase diagram for the $\text{AgI}\text{Ag}{}_4\text{P}{}_2\text{O}{}_7$ system of fast-ion electrolyes is established along with the conductivity-composition relationship for polycrystalline samples. The highest conductivity compound (0.07 Ω^?1 cm^?1 at 300 K) has the composition Ag₁₆I₁₂P₂O₇. Measurements of relative permittivity and conductivity over a frequency range of 50 Hz to 100 kHz and a temperature range of 77 to 320 K on polycrystalline samples and single crystals of Ag₁₆I₁₂P₂O₇ show that the conductivity and its temperature dependence is anisotropic, with a higher conductivity along the c axis and a change in the activation energy for conduction from 0.4 eV at low temperatures to 0.14 eV above 300 K. Perpendicular to the c axis the activation energy is constant with temperature (0.28 eV). This anisotropy and a frequency dispersion in the ac conductivity between 110 to 150 K is shown to originate in the crystal structure of the material and in the distribution of Ag⁺ ions between different sites.